CN106574201A - 用于防止和除去内燃机中的碳沉积物的润滑剂 - Google Patents

用于防止和除去内燃机中的碳沉积物的润滑剂 Download PDF

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CN106574201A
CN106574201A CN201580029414.XA CN201580029414A CN106574201A CN 106574201 A CN106574201 A CN 106574201A CN 201580029414 A CN201580029414 A CN 201580029414A CN 106574201 A CN106574201 A CN 106574201A
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lubricant
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base oil
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CN106574201B (zh
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杨颖�
F·E·洛克伍德
D·J·多森
J·弗雷德里克
J·达施
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Shengpai Global Product Intellectual Property Co ltd
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Abstract

一种有效除去或防止内燃机中的碳沉积物的润滑剂配制物具有由苯胺点界定的约20到约115的溶解能力、小于15％的挥发度(如通过NOACK测量的)、高于40分钟的氧化稳定性(如通过PDSC测量的)以及高于2cSt但低于10cSt的基础油粘度。润滑剂配制物可以由第III、IV以及V组润滑剂，尤其是聚α烯烃、烷基萘与诸如多元醇酯的极性的第V组基础料的共混物形成。碳沉积物可以被通过用润滑剂简单地运转发动机持续一个所需的循环从发动机活塞除去，或可以连续用在发动机中以防止聚积。

Description

用于防止和除去内燃机中的碳沉积物的润滑剂
优先权要求
申请人要求享有2014年4月11日提交的美国临时专利申请序列号61/978,488的权益，该临时专利申请在此通过引用并入。
发明背景
可以形成在活塞和环上的沉积物有三种类型：淤泥、漆料以及硬碳。硬碳是最难除去的。经过一段时间，碳沉积物可以形成在某些内燃机上，尤其是活塞环岸上和环与活塞之间的槽内。这些碳沉积物使油耗增加而表现出它们的存在。碳沉积物可以造成活塞环粘住，这阻止活塞环形成合适的密封，合适的密封允许油进入燃烧室且允许燃烧产物进入油中。碳可以沉积在环与槽之间且沉积在环岸上，这对发动机造成不可避免的损坏。
内燃机中使用的典型的润滑剂被设计成延迟沉积物形成，但并没有除去随时间累积的碳聚积物。这与现代内燃机特别相关，在现代内燃机中额外的性能要求具有升高的活塞温度。
此外，用于内燃机的润滑剂必须与诸如发动机内的密封件的弹性体相容、具有可接受的防腐性、足以清洁发动机且不会呈现出过多的油耗。为了被用在柴油发动机中，所配制的润滑剂必须具有足够的去污力和分散性以通过特定制造商的规定所要求的多次发动机测试和/或美国石油学会“C”或“F”类关于柴油发动机油或ACEA(欧洲汽车制造商协会)柴油类别中类似的规定要求。然而，通过这些要求的规定所需的含灰组分通常恶化了沉积。因而，虽然可以使用常规的高苯胺点基础油(如天然气发动机中使用的某些油)产生具有低沉积倾向的发动机油，但这通常将不会通过关于与柴油发动机一起使用时的规定。此外，在本文规定的溶解能力的范围之外的这类油并不会具有清洁和释放活塞环的作用，由此减少油耗或防止油耗损失。
发明概述
本发明以实现下述目标为前提：润滑剂配制物可以起到防止和/或除去内燃发动机中的碳聚积的作用。
具体地，由第III组、第IV组以及第V组基础油的共混物形成的润滑剂配制物可以有效防止碳聚积并除去碳聚积，这样的基础油具有所定义的基础油的溶解能力、低于所定义的阈值(15％，如通过NOACK测量的)的挥发度、最低的氧化稳定性(高于40分钟，如通过PDSC测量的)以及约2到约10cSt的基础油粘度(100℃下测量的运动粘度)。溶解能力可以通过各种方法进行测量，例如苯胺点之类的。具有苯胺点为20-115且优选60的基础油共混物的润滑剂配制物应该足够除去发动机中的碳聚积且仍呈现出弹性体相容性。
基础油配制物通过以确立有效的溶解能力、挥发度、氧化稳定性以及基础油粘度的相对量共混第III组和/或第IV组基础油与来自第V组的较高溶解能力的基础油来形成，同时保持与弹性体的相容性，提供了可接受的防腐性并清洁发动机而没有过多的油耗。
鉴于下面的详述和附图的简述，本发明的目的和优势将得到进一步的理解。
附图简述
图1是显示了各种充分配制的发动机油的苯胺点随基础油混合物中的第V组的百分数变化的图；
图2是显示了各种充分配制的发动机油的苯胺点随基础油混合物中的第V组的百分数变化的图；以及
图3是比较市售的油相对于本发明的油的油耗的图。
发明详述
本发明的润滑剂包括基础油共混物，其是不同基础料与通常存在于内燃机用的润滑剂配制物中的典型添加剂组合的混合物。两种或更多种类型的基础油的共混物的基础油被一起共混以确立足以控制/除去碳沉积物的溶解能力。在本发明中，溶解能力可以被以不同方式定义。一种定义溶解能力的方式是苯胺点。苯胺点是等体积的苯胺与样品的最低平衡溶液温度。在此情形中，样品将是基础油共混物。应注意到，当规定期望的基础油共混物的苯胺点的范围时，应理解，配制物的至多25％可以由其他添加剂组成。添加剂通常在至多50％的基础油中携载。因而，配制物中的所有基础油，包括添加有添加剂的基础油应该具有下文规定的苯胺点。
苯胺点的具体测试方法描述在ASTM D 611中。对于本发明中的应用来说，苯胺点以摄氏度来定义。对于本发明中的应用来说，基础油应该具有等同于20-115的苯胺点的溶解能力。然而，溶解能力不能够大到使得基础油与弹性体不相容。通常，发现由苯胺点定义的50到95或55到80特别是约60的溶解能力有效用于本发明。
第III组和/或第IV组基础油与第V组基础油组合形成具有期望的苯胺点的基础油。(基础油组的参数由美国石油学会定义，)这通过图1显示的数据证明，图1显示了基础油和它们的苯胺点的不同组合。图2显示了第V组基础油与PAO的组合的苯胺点数据。
挥发度对有效地润滑发动机也是关键的。通常，对于本发明的应用来说，如通过NOACK测量的挥发度必须小于15％且优选小于10％以及通常8％或更小。这通过优化第III组、第IV组以及第V组基础油的平衡来控制。
除了挥发度外，所配制的油必须呈现出可接受的氧化稳定性。如通过压差扫描量热法ASTM D6186测量的(本申请中的数据是使用PDSC与加压空气，而不是加压氧气获得的)PDSC，应该具有40分钟的最小值，优选高于60分钟，更优选高于80分钟且最优选高于100分钟。合适基础料的选择对其有所促进，尤其是来自第V组的基础料。
优选地，基础油将具有大于120，优选大于135且更优选150或更大的粘度指数。
最终，由D445(100℃下的运动粘度)测量的基础油粘度应该低于10厘斯，优选低于8且高于约2厘斯。而且，合适基础油的选择将界定粘度。
此外，所配制的油应该具有在热氧化发动机油模拟测试33C(ASTM D6335)中小于20mg的沉积速率。需要看待总沉积物以及其他标准，诸如苯胺点和前面关于良好性能描述的其他参数。
本发明的润滑剂配制物通常将由来自第III组、第IV组以及第V组中的至少两种的基础油的共混物形成。本发明中的第III组、第IV组以及第V组基础油指的是美国石油学会关于类别III、IV以及V的定义。第IV组基础油主要包括聚α烯烃基础油(PAO)。可以用在本发明中的优选的聚α烯烃基础油可以从直链C2到C32，优选C6到C16α烯烃获得。α烯烃的特别优选的原料是1-辛烯、1-癸烯、1-十二烯以及1-十四烯。
适合于形成本发明的基础油共混物的第III组基础油包括例如GTL(气体到液体)基础料以及在满足API的第III组类别的硫含量、饱和物含量以及粘度指数要求的严苛的加氢处理下形成的基础料。
通常，可降低基础油的苯胺点且适合于用在内燃机中的任何第V组基础油可以被用在本发明中。应注意到，低粘度指数的基础油诸如环烷烃和芳香族化合物提取物将增强溶解能力，但因它们差的氧化稳定性并不适合用在发动机油中。
合适的第V组基础油包括烷基化芳香族化合物、聚烷撑二醇以及酯基础油及其混合物。一种优选的烷基化芳香族化合物是烷基化萘。烷基化萘是被一个或更多个诸如甲基、乙基或丙基的短链烷基取代的萘。示例性的烷基取代的萘包括α甲基萘、二甲基萘以及乙基萘。Synestic是市售的烷基化萘。
第V组酯基础油包括但不限于不饱和酯、聚酯包括长链酯和二酯。合适的酯可以可以衍生自石油或有机材料前驱体诸如脂肪和植物油。可以用于替代酯的或除了酯之外的其他第V组润滑剂包括聚烷撑二醇以及在第V组类别下提供溶解能力、挥发度以及抗氧化性益处的新的合成基础料。
用于本发明的特别合适的酯润滑剂包括来自Croda International，PLC的以名称Priolube 1973市售的饱和多元醇酯。用在本发明中的其他合适的酯包括来自Oleon的以名称adialube获得的那些、来自Chemtura的以名称Hatcol获得的那些、来自BASF的以名称Cognis Synative获得的那些、来自Emery的以名称Emery获得的那些以及来自ExxonMobile的以名称Esterex获得的那些。通常，这些是通过C5-C25酸与C5-C24二醇的反应形成的酯。
在选择基础油的具体组分时，如通过ASTM 2270测量的，如果要选择极性更强的多元醇酯，那么为了维持与发动机内的弹性体的相容性，将需要减少多元醇酯的量。换句话说，如果如由苯胺点定义的溶解能力或溶解能力的其他量度是过大的(苯胺点过低)，那么发动机中的密封件可能被润滑剂配制物破坏且开始渗漏，还可能过早出现腐蚀。可以使用通过密封件测试ASTM-D7216的任何基础油共混物。
而且，为了改进燃料经济性，期望低苯胺点的第V组基础油，即基础油的极性部分，以具有比诸如PAO的石蜡族分子高的粘度，通常高4-5cSt。
在根据本发明的一个实施方案中，润滑剂配制物包括酯基油、烷基化萘以及PAO。PAO提供了润滑性和氧化稳定性，但却对溶解能力几乎没有任何贡献(如果有的话)。第III组基础油可以用于替代PAO。烷基化萘提供了氧化稳定性，贡献了溶解能力以及贡献了必要的粘度。优选地，多元醇酯改进了基础油混合物的溶解能力。这些酯连同烷基化萘将以有效确立具有20到115之间且优选50到95之间的苯胺点的溶解能力的量被添加。如图1所示，具有20％，优选30％的多元醇酯且其余为PAO的配制物具有有利的苯胺点。多元醇酯的上限值由其他性能特征决定且通常将不会超过80％。
在一个实施方案中，润滑剂配制物可以包括约30-60％的多元醇酯(尤其是Priolube 1973)、10％的烷基化萘以及10-40％的PAO。
通常，配制物将包括汽车和柴油发动机应用中通常存在的润滑剂添加剂，被称为添加剂包(additive package)。这些可以包括但不限于氧化抑制剂、分散剂、金属和非金属洗涤剂、缓蚀剂和阻锈剂诸如硼酸酯、金属钝化剂、耐磨剂、极压添加剂、倾点下降剂、粘度调节剂、密封相容剂、摩擦改进剂、消泡剂、破乳剂以及其他的。除了添加剂包中的无灰分散剂和胺类(aminic)抗氧化剂外，可以以按重量计油的2％的量添加补充的无灰TBN(酸中和剂)。
表I显示了四种示例性配制物和物理数据。
表I
在使用本发明的配制物释放活塞环并除去先前聚积在发动机活塞上的碳沉积物时，发动机中的油被排空并用具有显著溶解能力诸如具有约60的苯胺点的配制物替换。发动机被运行，直至油需要被再次替换，这通常是交通工具中的柴油发动机运转至少30,000英里而汽油发动机运转5000英里。一旦需要替换油，那么可以用标准发动机油配制物进行替换。此油排空的益处由比较排空之前和之后的发动机中的油耗决定。在现场测试中，发现改进的油耗(减少的油耗)在8类卡车中高达179％且在具有先前高沉积物和高油耗的8类发动机的静止发动机测试中高达275％。
图3显示了使用市售的油和表I中的配制物4的油耗的比较。油耗通常与发动机沉积物形成有关。图3中的数据验证了因使用本发明的油而降低了油耗。
具有由苯胺点定义的约110，优选约90的溶解能力的配制物在防止碳聚积方面是有效的，且很显然，如果正如发动机制造商所要求的，按一定的时间间隔用新的润滑剂替换的话，那么配制物简直能够连续用于发动机的整个寿命期。一种这样的配制物是配制物#3。
另外的配制物显示在表II中。式#9被包括在内以阐释具有太多非极性基础油(在此情形中>80％的PAO6)的配制物将超过苯胺点及因此的期望的溶解能力和本发明主题的沉积物。
表II
因而，本发明的配制物用于防止和/或除去发动机活塞上的碳沉积物并保持和/或释放活塞环。然而，配制物同时还满足发动机的必要的弹性体相容性、油耗、清洁度以及防腐要求。
这是本发明连同实施本发明的优选方法的描述，其中本发明本身应该仅由要求保护的所附权利要求界定。

Claims (15)

1.一种润滑剂配制物，具有高于40分钟的氧化稳定性(通过PDSC测量的)和小于15％的挥发度(通过NOACK测量的)；
所述配制物包括由至少两种基础油形成的基础油共混物，所述基础油的组选自具有由苯胺点定义的20到115的溶解能力和100℃下约2cSt到约10cSt的粘度(如通过ASTM D445测量的)的第III组、第IV组以及第V组。
2.如权利要求1所述的组合物，其中所述基础油共混物包括聚α烯烃和粘度高于所述聚α烯烃的极性基础油。
3.如权利要求1所述的润滑剂，其具有包括硼酸酯的添加剂包。
4.如权利要求2所述的润滑剂，其中所述极性基础油是极性酯，其中所述极性酯在100℃下的运动粘度大于5cSt。
5.如权利要求1所述的润滑剂，其通过ASTM法2270得到的基础油混合组合物的粘度指数大于20。
6.如权利要求5所述的润滑剂，其具有大于150的粘度指数。
7.如权利要求1所述的润滑剂，除了无灰分散剂和胺类抗氧化剂之外，其包括在最终组合物的0.1％到2％范围内的补充的无灰TBN(酸中和剂)。
8.如权利要求1所述的组合物，其包括聚α烯烃、烷基化萘和多元醇酯的基础油共混物。
9.如权利要求2所述的组合物，其中所述极性基础油包括选自由多元醇酯、二酯、聚烷撑二醇、长链酯及其组合组成的组的油。
10.如权利要求1所述的润滑剂配制物，具有小于10％的挥发度和小于20mg的TEOST33。
11.如权利要求10所述的润滑剂配制物，具有按重量计20％到约80％的第V组和按重量计约80％到20％的PAO的基础油共混物。
12.如权利要求10所述的润滑剂配制物，其中所述基础油共混物具有20℃-95℃的苯胺点。
13.如权利要求12所述的润滑剂配制物，其中所述基础油共混物具有50℃-95℃的苯胺点。
14.如权利要求13所述的润滑剂配制物，具有至少100分钟的PDSC。
15.如权利要求11所述的润滑剂配制物，其中所述PAO具有第一粘度，所述第V组基础油具有第二粘度，所述第二粘度大于所述第一粘度。
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CN115368957A (zh) * 2019-08-14 2022-11-22 胜牌许可和知识产权有限公司 含有无灰tbn分子的润滑剂组合物
CN115368957B (zh) * 2019-08-14 2023-10-13 胜牌全球产品知识产权有限公司 含有无灰tbn分子的润滑剂组合物

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